The kinetics of the oxidation of ammonia by nitrous oxide

1964 ◽  
Vol 17 (2) ◽  
pp. 202 ◽  
Author(s):  
TN Bell ◽  
JW Hedger
Keyword(s):  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Free Radical ◽  
Rate Equation ◽  
Radical Mechanism ◽  
15N Isotope ◽  
Free Radical Mechanism ◽  
Products Of Reaction ◽  
Kinetics Of ◽  
Decomposition Of Nitrous Oxide

Ammonia is oxidized by nitrous oxide smoothly and homogeneously at temperatures between 658 and 730� and total pressures up to 250 mm. The products of reaction, nitrogen, water, and hydrazine are accounted for by a free-radical mechanism initiated by oxygen atoms which result from the thermal decomposition of nitrous oxide. Ammonia labelled with the 15N-isotope was used to distinguish between the nitrogen formed from the nitrous oxide and that from the ammonia. The kinetics follow an empirical rate equation, ������������� Rate = k'[N2O]1.56 + k"[N2O]0.61[NH3]. This is of a form which shows the importance of the ammonia molecule participating in the activation of nitrous oxide through bimolecular collision. Assigning a collisional efficiency of unity for like N2O-N2O collisions, the efficiency of ammonia in the process ������������ NH3 + N2O → NH3 + N2O* is determined as 0.85.

THE DECOMPOSITION OF NITROUS OXIDE ON A SILVER CATALYST

1937 ◽  
Vol 15b (6) ◽  
pp. 237-246 ◽  
Author(s):  
E. W. R. Steacie ◽  
H. O. Folkins
Keyword(s):  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Rate Equation ◽  
Platinum Catalyst ◽  
Silver Catalyst ◽  
Kinetics Of ◽  
Decomposition Of Nitrous Oxide

The kinetics of the thermal decomposition of nitrous oxide on a silver catalyst has been investigated. The rate of the reaction can be expressed by the equation[Formula: see text]It may therefore be concluded that the nitrous oxide is slightly adsorbed by the catalyst, while oxygen is fairly strongly adsorbed and retards the reaction. Added oxygen affects the reaction in the manner predicted by the rate equation, in contrast to its behavior on a platinum catalyst as previously found by Steacie and McCubbin.

Thermal decomposition of alcohols. II. 2-Methylpropan-2-ol

1975 ◽  
Vol 28 (8) ◽  
pp. 1725 ◽  
Author(s):  
WD Johnson
Keyword(s):  
Thermal Decomposition ◽  
Free Radical ◽  
Arrhenius Equation ◽  
Initial Rate ◽  
Radical Mechanism ◽  
Reaction Products ◽  
Radical Process ◽  
First Order ◽  
Free Radical Mechanism

The thermal decomposition of 2-methylpropan-2-ol has been investigated from 503 to 612�C, over initial pressures ranging from 40 to 275 mm and in the presence of toluene from 520 to 602�C. The decomposition is homogeneous and first order with respect to the initial concentrations of alcohol giving the Arrhenius equation (R = 8.31 J mol-1 K-1) �������������������������� K=1012.7exp(-249,800/RT) s-1 for the initial rate. The decomposition of this alcohol is inhibited by the reaction products, mainly 2-methylpropene, and by the addition of toluene. There are contributions from the unimolecular elimination of water (k = 1013.6exp(-268,000/RT)s-1) and from a flee radical process (k = 1011.0 x exp(-227,000/RT) s-1). A free radical mechanism, which explains the minor products of the reaction and the varying results of other workers, is proposed.

The kinetics of the thermal decomposition of trifluoroacetaldehyde

1965 ◽  
Vol 18 (10) ◽  
pp. 1561 ◽  
Author(s):  
NL Arthur ◽  
TN Bell
Keyword(s):  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Rate Equation ◽  
Surface Effect ◽  
Inert Gases ◽  
Radical Chain ◽  
Small Surface ◽  
Experimental Rate ◽  
Products Of Reaction ◽  
Kinetics Of

The thermal decomposition of trifluoroacetaldehyde has been studied at temperatures between 471� and 519�, and at pressures up to 180 mm. The main products of reaction are trifluoromethane and carbon monoxide in equal amounts; small amounts of hexafluoroethane and hydrogen are also formed. The experimental rate equation governing the observed kinetics is of the form Rate = k?[CF3CHO]3/2, where k? = 1012.2exp(-49000/RT) l.� mole-1 sec-1 A small surface effect is apparent, an increase in surface area causing an increase in rate. Inert gases, namely carbon monoxide and dioxide, increase the rate of decomposition, the experimental rate equation assuming the form Rate = (k'[CF3CHO]3 + k"[CF3CHO]2.2[M])� A mechanism is proposed which predict,^ the experimental form of the rate equation and involves initiation through a second-order energy transfer process followed by a radical chain mechanism, the length of which is 1200 with P(CF3CHO) = 200 mm. Termination is considered to be through the third-order recombination of trifluoromethyl radicals.

Stoichiometry and Kinetics of the Cobalt(III) Oxidation of Acetamide, Formamide, N-Methylformamide and N,N-Dimethylformamide in Acid Perchlorate Solutions

1979 ◽  
Vol 32 (3) ◽  
pp. 537 ◽  
Author(s):  
F Ahmad ◽  
VS Baswani
Keyword(s):  
Free Radical ◽  
Perchloric Acid ◽  
Activation Energies ◽  
Radical Mechanism ◽  
Rate Law ◽  
Free Radical Mechanism ◽  
Kinetics Of

The oxidation of acetamide, formamide, N-methylformamide and N,N-dimethylformamide by cobalt(III) in perchloric acid at 20°C has been investigated. The reaction requires nearly three moles of cobalt(III) for one mole of amide (except acetamide) and nearly one mole of cobalt(III) is consumed per mole of acetamide, and leads in each case to the formation of the respective amines. The oxidation of the amides is found to obey the rate law -d[CoIII]/dt = (k' + k''[H+])[Co3+] A free-radical mechanism has been proposed for the reaction. Activation energies and entropies are calculated for each reaction.

Comparative QSAR evidence for a free-radical mechanism of phenol-induced toxicity

2000 ◽  
Vol 127 (1) ◽  
pp. 61-72 ◽  
Author(s):  
Corwin Hansch ◽  
Susan C. McKarns ◽  
Carr J. Smith ◽  
David J. Doolittle
Keyword(s):  
Free Radical ◽  
Radical Mechanism ◽  
Free Radical Mechanism

Dirhodium(II)-Catalyzed Diamination Reaction via a Free Radical Pathway

2021 ◽  
Author(s):  
Zhiying Fan ◽  
Zhifan Wang ◽  
Ruoyi Shi ◽  
Yuanhua Wang
Keyword(s):  
Free Radical ◽  
Bond Formation ◽  
Mechanistic Study ◽  
Radical Mechanism ◽  
Free Radical Mechanism

Unlike C-N bond formation with classical dirhodium(II)-nitrenoids as the key intermediate, dirhodium(II)-catalyzed 1,2-and 1,3-diamination reactions are realized by a free radical mechanism. A mechanistic study revealed that the reactions undergo...

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